CN111992232A - Supported transition metal carbide and preparation method and application thereof - Google Patents
Supported transition metal carbide and preparation method and application thereof Download PDFInfo
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- CN111992232A CN111992232A CN202010898043.1A CN202010898043A CN111992232A CN 111992232 A CN111992232 A CN 111992232A CN 202010898043 A CN202010898043 A CN 202010898043A CN 111992232 A CN111992232 A CN 111992232A
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- transition metal
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- oxalic acid
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 94
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 114
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000003054 catalyst Substances 0.000 claims abstract description 61
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
- -1 transition metal salt Chemical class 0.000 claims abstract description 17
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 238000010000 carbonizing Methods 0.000 claims abstract description 3
- 238000004729 solvothermal method Methods 0.000 claims abstract description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 315
- 235000006408 oxalic acid Nutrition 0.000 claims description 105
- 238000006243 chemical reaction Methods 0.000 claims description 64
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims description 22
- 239000004021 humic acid Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 239000000356 contaminant Substances 0.000 claims description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000008103 glucose Substances 0.000 claims description 8
- 239000004005 microsphere Substances 0.000 claims description 8
- 229910001567 cementite Inorganic materials 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical group C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical group [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 4
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910026551 ZrC Inorganic materials 0.000 claims description 2
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- GVEHJMMRQRRJPM-UHFFFAOYSA-N chromium(2+);methanidylidynechromium Chemical compound [Cr+2].[Cr]#[C-].[Cr]#[C-] GVEHJMMRQRRJPM-UHFFFAOYSA-N 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- UNASZPQZIFZUSI-UHFFFAOYSA-N methylidyneniobium Chemical compound [Nb]#C UNASZPQZIFZUSI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 229910003470 tongbaite Inorganic materials 0.000 claims description 2
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 abstract description 14
- 239000010865 sewage Substances 0.000 abstract description 9
- 238000007348 radical reaction Methods 0.000 abstract description 8
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- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 48
- 239000007789 gas Substances 0.000 description 43
- 238000006385 ozonation reaction Methods 0.000 description 20
- 230000003197 catalytic effect Effects 0.000 description 19
- 230000008569 process Effects 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 230000003647 oxidation Effects 0.000 description 16
- 239000002244 precipitate Substances 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 230000035484 reaction time Effects 0.000 description 11
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 10
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 10
- 238000005273 aeration Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
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- 229910052593 corundum Inorganic materials 0.000 description 5
- 239000010431 corundum Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
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- 239000000126 substance Substances 0.000 description 4
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- 238000012546 transfer Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
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- 230000000977 initiatory effect Effects 0.000 description 2
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- 238000003911 water pollution Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001500 aryl chlorides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
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- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
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- 230000004083 survival effect Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a supported transition metal carbide and a preparation method and application thereof, belonging to the technical field of catalysts. The preparation method of the supported transition metal carbide comprises the following steps: dissolving a carbon source and a transition metal salt in a solvent, carrying out solvothermal reaction to prepare a metal organic framework precursor, and then carbonizing to obtain the metal organic framework precursor. The supported transition metal carbide is used as a catalyst to catalyze the ozone oxidation reaction of organic matters in water, so that the free radical reaction is initiated, the removal rate of the organic matters in the sewage is high, the removal rate is high, the mineralization degree is high, and the organic pollutants with complex types in the water can be selectively catalyzed and oxidized; meanwhile, when the catalyst is used, the ozone oxidation reaction can be carried out at room temperature, the time consumption is short, and the energy consumption is low; in addition, the preparation process of the load type transition metal carbide is simple and easy to form. The load type transition metal carbide can be used as a catalyst to relieve the problems of environment and energy, has strong practicability and good market prospect.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a supported transition metal carbide and a preparation method and application thereof.
Background
With the rapid development of the industrialization process, the water pollution problem becomes more and more serious, and the water pollution problem has a great threat to the survival safety of human beings. At present, about 20 percent of people in the world cannot obtain safe domestic water meeting basic living needs, and a plurality of countries have the phenomena of water resource shortage and unbalanced utilization. According to the Chinese environmental condition bulletin, five of offshore waters and seven water systems in China are polluted to different degrees. The sewage in the new situation has wide sources, complex components and poor biodegradability, and the problems bring unprecedented challenges to the traditional water treatment process. How to effectively realize sewage purification is the first challenge to meet the water resource shortage.
The ozonization technology can not only kill common bacteria and viruses, but also oxidize organic matters which are difficult to be biochemically degraded in the sewage, and has obvious advantages in the deep water treatment process. During the ozonization process, part of the ozone is blown off, and the rest of the ozone reacts with the organic matter by means of both direct oxidation and indirect oxidation. The direct oxidation process is highly selective and produces small molecular aldehydes or carboxylic acid by-products. The path of the indirect oxidation reaction is a free radical reaction, and free radicals generated in the process can indiscriminately oxidize various organic matters in the water and achieve thorough mineralization. Therefore, the ozone utilization rate of the indirect oxidation route is much higher than that of the direct oxidation route. In summary, the research and development of the high-efficiency catalyst capable of enhancing mass transfer and initiating indirect oxidation reaction can improve the water treatment effect and reduce the water treatment cost.
Transition metal catalysts have attracted great attention as a new class of catalytic materials. Among them, the transition metal carbide exhibits excellent catalytic activity and selectivity in catalytic hydrogenation, paraffin isomerization, dehydrogenation, desulfurization, denitrification, reforming, i.e., oxidation reaction, and the like. However, the transition metal catalyst has problems of high price, non-reusability, difficult product separation, trace transition metal catalyst residue in the product, and the like in the using process. The supported transition metal catalyst can solve the problem of difficult product separation while obtaining the effect equivalent to that of the transition metal catalyst, and can be recycled.
The supported transition metal catalysts mainly comprise the following components: (1) inorganic oxide carrier supported transition metal catalyst; (2) an activated carbon-supported transition metal catalyst; (3) an organic carrier supports a transition metal catalyst; (4) transition metal catalyst supported by organic-inorganic hybrid material carrier; (5) a magnetic nanoparticle-supported transition metal catalyst. Although these supported transition metal catalysts can solve some problems of the transition metal catalysts, such as difficult product separation, inability to reuse, etc., they also have many disadvantages, such as further improvement of the activity of the catalysts.
Meanwhile, one supported transition metal catalyst is not suitable for all types of reactions, and in 1994, Marck et al reported Suzuki coupling reactions using an activated carbon supported transition metal catalyst (Pd/C catalyst): when brominated aromatics are used as substrates, the Pd/C catalyst can catalyze the reaction well, but when aryl chlorides are used, the yield is low. It can be seen that the range of use of different catalysts is different.
At present, the ozone oxidation reaction of organic pollutants in sewage by efficiently catalyzing the organic pollutants by using transition metal carbide is not seen. The ozone oxidation reaction of organic pollutants in sewage efficiently catalyzed by the load type transition metal carbide is not shown.
Disclosure of Invention
The invention aims to provide a supported transition metal carbide catalyst and a preparation method and application thereof.
The invention provides a preparation method of supported transition metal carbide, which comprises the following steps: dissolving a carbon source and a transition metal salt in a solvent, carrying out solvothermal reaction to prepare a metal organic framework precursor, and then carbonizing to obtain the metal organic framework precursor.
Further, the air conditioner is provided with a fan,
the carbon source is one or two of glucose, melamine or terephthalic acid;
and/or in the transition metal salt, the transition metal is vanadium, tungsten, iron, titanium, chromium, zirconium or niobium;
and/or the solvent is deionized water, ethanol or N, N-dimethylformamide;
and/or the mass ratio of the carbon source to the transition metal salt is 1: (0.05-0.5);
and/or the mass volume ratio of the carbon source to the solvent is (1-5) g: (10-100) mL.
Further, the air conditioner is provided with a fan,
the carbon source is glucose;
and/or the transition metal salt is ammonium metavanadate, phosphotungstic acid, ferric nitrate, titanium tetrachloride, chromium chloride, zirconium chloride or niobium chloride;
and/or the solvent is deionized water;
and/or the mass ratio of the carbon source to the transition metal salt is 1: (0.1 to 0.3);
and/or the mass volume ratio of the carbon source to the solvent is 1 g: 10 mL.
Further, the air conditioner is provided with a fan,
the transition metal salt is ammonium metavanadate;
and/or the mass ratio of the carbon source to the transition metal salt is 1: (0.12-0.27).
Further, the air conditioner is provided with a fan,
when the mixture is dissolved in the solvent, the temperature of the solvent is 50-100 ℃, and the mixture is stirred for 1-5 hours;
and/or the hydrothermal reaction condition is that the reaction is carried out for 12-24 hours at the temperature of 140-220 ℃;
and/or cleaning and drying the prepared metal organic framework precursor after the hydrothermal reaction;
and/or the carbonization condition is carbonization in an inert atmosphere.
The invention also provides a supported transition metal carbide which is a transition metal carbide nanoparticle supported on the carbon microsphere carrier.
Further, the supported transition metal carbide is prepared by the preparation method.
The invention also provides the use of the supported transition metal carbide as a catalyst: the catalyst is used for catalyzing the ozone oxidation reaction of organic pollutants in water;
preferably, the organic contaminants are selected from phenolic and/or carboxylic organic contaminants;
more preferably, the organic contaminant is oxalic acid and/or humic acid.
The invention also provides the application of the supported transition metal carbide in preparing the catalyst, which comprises the following steps: the catalyst is used for catalyzing the ozone oxidation reaction of organic pollutants in water;
preferably, the organic contaminants are selected from phenolic and/or carboxylic organic contaminants;
more preferably, the organic contaminant is oxalic acid and/or humic acid.
The invention also provides the use of a transition metal carbide as a catalyst and/or in the preparation of a catalyst: the catalyst is used for catalyzing the ozone oxidation reaction of organic pollutants in water;
preferably, the organic contaminants are selected from phenolic and/or carboxylic organic contaminants;
and/or the transition metal carbide is vanadium carbide, tungsten carbide, iron carbide, titanium carbide, chromium carbide, zirconium carbide or niobium carbide;
more preferably, the organic contaminant is oxalic acid and/or humic acid;
and/or the transition metal carbide is vanadium carbide.
In the catalytic ozonation treatment process of the organic sewage, the use temperature of the catalyst is 15-30 ℃, the introduced atmosphere is the mixed atmosphere of oxygen and ozone, and organic pollutants in water can be organic matters such as phenol or carboxylic acid.
The load type transition metal carbide has the following beneficial effects:
(1) the invention provides a simple preparation method of ultra-small transition metal carbide nanoparticles (with the diameter of about 5 nm), and the prepared supported transition metal carbide nanoparticles are dispersedly supported on the surface of carbon microspheres (with the diameter of about 150 nm). The small size effect and the surface effect make the catalyst have more efficient catalytic activity.
(2) Compared with the independent ozone oxidation reaction in which non-supported transition metal carbide and carbon microsphere materials are used as catalysts and no catalysts are added, the ozone oxidation reaction of the organic pollutants in the wastewater by adopting the supported transition metal carbide to catalyze the ozone oxidation reaction of the organic pollutants in the water has the advantages of high removal rate of the organic matters in the wastewater and high effluent quality (less residual organic matters in the effluent).
(3) The catalyst developed by the invention takes transition metal carbide such as vanadium carbide, tungsten carbide or iron carbide and the like as active components, the carbon carrier is prepared by a metal organic framework precursor obtained by the thermal reaction of a high-temperature carbonization solvent, and the preparation process of the catalyst is simple and easy to mold, and has the economical efficiency of industrial application.
(4) In the invention, when the supported transition metal carbide catalyzes the ozone oxidation reaction of organic matters in water, a free radical reaction (indirect oxidation path) can be initiated, the removal rate of organic pollutants is high, the mineralization degree is high, and the supported transition metal carbide can indiscriminately catalyze the oxidation removal of complex organic matters in water; the reaction can be carried out at room temperature, and the energy consumption of the process is low; the catalytic ozonation process can alleviate environmental and energy problems.
In conclusion, when the supported transition metal carbide is used as a catalyst to catalyze the ozone oxidation reaction of organic matters in water, a free radical reaction is initiated, the removal rate of the organic matters in the sewage is high, the removal rate is high, the mineralization degree is high, and the organic pollutants with complex types in the water can be selectively catalyzed and oxidized; meanwhile, when the catalyst is used, the ozone oxidation reaction can be carried out at room temperature, the time consumption is short, and the energy consumption is low; in addition, the preparation process of the load type transition metal carbide is simple and easy to form. The load type transition metal carbide can be used as a catalyst to relieve the problems of environment and energy, has strong practicability and good market prospect.
Obviously, many modifications, substitutions, and variations are possible in light of the above teachings of the invention, without departing from the basic technical spirit of the invention, as defined by the following claims.
The present invention will be described in further detail with reference to the following examples. This should not be construed as limiting the scope of the above-described subject matter of the invention or to the following examples only. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Drawings
FIG. 1 is V8C7SEM picture of/CS.
FIG. 2 is V8C7Characterization of/CS: a is V8C7TEM picture of/CS; b is V8C7V in/CS8C7The particle size statistics of (a); c is V8C7HRTEM picture of/CS; d is V8C7V in/CS8C7The lattice diffraction pattern of (1).
FIG. 3 is V8C7XRD pattern of/CS.
FIG. 4 shows the results of the ozonation reaction of oxalic acid in water.
FIG. 5 is a comparison of ozone utilization in the oxidation reaction of oxalic acid in water.
FIG. 6 shows the results of the ozone oxidation reaction alone and the catalytic ozone oxidation reaction of the mixed solution of oxalic acid and humic acid.
Detailed Description
The raw materials and equipment used in the embodiment of the present invention are known products and obtained by purchasing commercially available products.
Example 1 preparation and catalytic Oxidation of Supported transition Metal carbides according to the invention
Supported transition metal carbide V8C7Preparation of/CS: will react0.47g of ammonium metavanadate (NH)4VO3) And 4.0g glucose (C)6H12O6) Added to 40ml of deionized water at 60 ℃ and stirred continuously for 1 hour at a constant temperature. The obtained mixture was added to a 60ml hydrothermal reaction kettle, and the stainless steel jacket of the hydrothermal reaction kettle was installed. And (3) placing the hydrothermal reaction kettle in an oven at 160 ℃ for reaction for 15 h. And after natural cooling, alternately cleaning the mixture for a plurality of times by using deionized water and ethanol, and centrifugally separating to obtain a brown precipitate (a metal organic framework precursor). Drying the precipitate in a vacuum oven at 70 deg.C, loading the obtained dried precipitate into a corundum boat, and placing in the center of a tube furnace. Heating to 1000 ℃ at a speed of 10 ℃/min in Ar gas flow of 40ml/min, preserving heat for 3h, and then naturally cooling. Grinding the obtained black substance into powder to obtain the load type vanadium carbide, marked as V8C7and/CS. FIG. 1 is V8C7SEM picture of/CS. FIG. 2a is V8C7TEM image of/CS, FIG. 2b is V8C7V in/CS8C7FIG. 2c is a graph V8C7HRTEM picture of/CS, V in FIG. 2d8C7V in/CS8C7The lattice diffraction pattern of (1). FIG. 3 is V8C7XRD pattern of/CS.
V8C7CS catalyzing the ozone oxidation reaction of oxalic acid in water: taking 1L of oxalic acid solution with the concentration of 50mg/L, adding the oxalic acid solution into a 1.5L reaction kettle, and starting a stirring device at the speed of 150 r/min. Then 50mg V is weighed8C7adding/CS into a reaction kettle, stirring and adding V8C7the/CS was rapidly and homogeneously dispersed in the solution. Pure oxygen (flow rate 200ml/min) passes through an ozone generator to generate a mixed gas of oxygen and ozone, and the concentration of ozone in the mixed gas is 4.2 mg/L. The mixed gas is blown into the oxalic acid solution from the bottom of the reaction kettle through an aeration device, and the ozone blown into the oxalic acid solution is 50.4 mg/h. When the mixed gas is introduced, timing is started, ozone enters a reaction system at the moment, and the ozone oxidation reaction of the oxalic acid starts to occur. The reaction temperature is 20 ℃, the reaction time is 60min, and the oxalic acid removal rate is 95%.
Example 2 preparation of Supported transition Metal carbide and catalytic Oxidation reactionSupported transition metal carbide W2C/CS preparation: 1.07g of phosphotungstic acid (H) was added to the reaction mixture3PW12O40) And 4.0g glucose (C)6H12O6) Added to 40ml of deionized water at 60 ℃ and stirred continuously for 1 hour at a constant temperature. The obtained mixture was added to a 60ml hydrothermal reaction kettle, and the stainless steel jacket of the hydrothermal reaction kettle was installed. And (3) placing the hydrothermal reaction kettle in an oven at 160 ℃ for reaction for 15 h. And after natural cooling, alternately cleaning the mixture for a plurality of times by using deionized water and ethanol, and centrifugally separating to obtain a brown precipitate (a metal organic framework precursor). Drying the precipitate in a vacuum oven at 70 deg.C, loading the obtained dried precipitate into a corundum boat, and placing in the center of a tube furnace. Heating to 1000 ℃ at a speed of 10 ℃/min in Ar gas flow of 40ml/min, preserving heat for 3h, and then naturally cooling. Grinding the obtained black substance into powder to obtain the load type tungsten carbide, which is marked as W2C/CS。
W2C/CS catalyzes the ozone oxidation reaction of oxalic acid in water: taking 1L of oxalic acid solution with the concentration of 50mg/L, adding the oxalic acid solution into a 1.5L reaction kettle, and starting a stirring device at the speed of 150 r/min. Then 50mg of W is weighed2Adding C/CS into a reaction kettle, and stirring W2The C/CS is rapidly and uniformly dispersed in the solution. Pure oxygen (flow rate 200ml/min) passes through an ozone generator to generate a mixed gas of oxygen and ozone, and the concentration of ozone in the mixed gas is 4.2 mg/L. The mixed gas is blown into the oxalic acid solution from the bottom of the reaction kettle through an aeration device, and the ozone blown into the oxalic acid solution is 50.4 mg/h. When the mixed gas is introduced, timing is started, ozone enters a reaction system at the moment, and the ozone oxidation reaction of the oxalic acid starts to occur. The reaction temperature is 20 ℃, the reaction time is 60min, and the oxalic acid removal rate is 94%.
Example 3 preparation and catalytic Oxidation of Supported transition Metal carbides according to the invention
Supported transition metal carbide Fe3C/CS preparation: 1.08g of the reaction mass are mixed with iron nitrate (Fe (NO)3)3) And 4.0g glucose (C)6H12O6) Added to 40ml of deionized water at 60 ℃ and stirred continuously for 1 hour at a constant temperature. Adding the obtained mixture into a 60ml hydrothermal reaction kettle, and installing the hydrothermal reaction kettleThe stainless steel jacket. And (3) placing the hydrothermal reaction kettle in an oven at 160 ℃ for reaction for 15 h. And after natural cooling, alternately cleaning the mixture for a plurality of times by using deionized water and ethanol, and centrifugally separating to obtain a brown precipitate (a metal organic framework precursor). Drying the precipitate in a vacuum oven at 70 deg.C, loading the obtained dried precipitate into a corundum boat, and placing in the center of a tube furnace. Heating to 850 ℃ at a speed of 10 ℃/min in Ar gas flow of 40ml/min, preserving heat for 3h, and then naturally cooling. Grinding the obtained black substance into powder to obtain the load type iron carbide, and marking as Fe3C/CS。
Fe3C/CS catalyzes the ozone oxidation reaction of oxalic acid in water: taking 1L of oxalic acid solution with the concentration of 50mg/L, adding the oxalic acid solution into a 1.5L reaction kettle, and starting a stirring device at the speed of 150 r/min. Then 50mg of Fe is weighed3C/CS is added into a reaction kettle, and Fe is stirred3The C/CS is rapidly and uniformly dispersed in the solution. Pure oxygen (flow rate 200ml/min) passes through an ozone generator to generate a mixed gas of oxygen and ozone, and the concentration of ozone in the mixed gas is 4.2 mg/L. The mixed gas is blown into the oxalic acid solution from the bottom of the reaction kettle through an aeration device, and the ozone blown into the oxalic acid solution is 50.4 mg/h. When the mixed gas is introduced, timing is started, ozone enters a reaction system at the moment, and the ozone oxidation reaction of the oxalic acid starts to occur. The reaction temperature is 20 ℃, the reaction time is 60min, and the oxalic acid removal rate is 92%.
Comparative example 1 catalysis of ozone oxidation reaction of oxalic acid in water by carbon microspheres
Preparation of the carbon microsphere CS: 4.0g of glucose (C)6H12O6) Added to 40ml of deionized water at 60 ℃ and stirred continuously for 1 hour at a constant temperature. The obtained solution was added to a 60ml hydrothermal reaction kettle, and the stainless steel jacket of the hydrothermal reaction kettle was installed. And (3) placing the hydrothermal reaction kettle in an oven at 160 ℃ for reaction for 15 h. And after natural cooling, alternately cleaning the mixture for a plurality of times by using deionized water and ethanol, and centrifugally separating to obtain a brown precipitate. Drying the precipitate in a vacuum oven at 70 deg.C, loading the obtained dried precipitate into a corundum boat, and placing in the center of a tube furnace. Heating to 1000 ℃ at a speed of 10 ℃/min in Ar gas flow of 40ml/min, preserving heat for 3h, and then naturally cooling. Grinding the obtained black substance into powder to obtain the carbon microsphere, which is recorded as CS.
The CS catalyzes the ozone oxidation reaction of oxalic acid in water: taking 1L of oxalic acid solution with the concentration of 50mg/L, adding the oxalic acid solution into a 1.5L reaction kettle, and starting a stirring device at the speed of 150 r/min. Then 50mg of CS is weighed and added into the reaction kettle, and the CS is rapidly and evenly dispersed in the solution under stirring. Pure oxygen (flow rate 200ml/min) passes through an ozone generator to generate a mixed gas of oxygen and ozone, and the concentration of ozone in the mixed gas is 4.2 mg/L. The mixed gas is blown into the oxalic acid solution from the bottom of the reaction kettle through an aeration device, and the ozone blown into the oxalic acid solution is 50.4 mg/h. When the mixed gas is introduced, timing is started, ozone enters a reaction system at the moment, and the ozone oxidation reaction of the oxalic acid starts to occur. The reaction temperature is 20 ℃, the reaction time is 60min, and the oxalic acid removal rate is 10%.
Comparative example 2 catalysis of ozonation of oxalic acid in Water by transition Metal carbide
Transition metal carbide V8C7The preparation of (1): 5.0g of commercial product V2The AlC maxene is soaked in 80mL of 40% HF solution and stirred at 200r/min for 48 h. Centrifuging the mixed solution at 3500r/min for 5min to separate out precipitate, repeatedly washing the precipitate with deionized water until pH reaches 6, and washing with anhydrous ethanol for 3 times. Washing, centrifuging to separate lower precipitate, drying in vacuum oven at 70 deg.C, and marking as V2C. Drying the obtained V2C placing the corundum boat in the center of a tube furnace at 15 vol% CH4Heating to 1000 ℃ at a speed of 10 ℃/min in Ar atmosphere, preserving heat for 3h, and then naturally cooling. Grinding the obtained black material into powder to obtain V8C7。
V8C7Catalyzing the ozone oxidation reaction of oxalic acid in water: taking 1L of oxalic acid solution with the concentration of 50mg/L, adding the oxalic acid solution into a 1.5L reaction kettle, and starting a stirring device at the speed of 150 r/min. Then 50mg V is weighed8C7Adding into a reaction kettle, stirring and stirring8C7Quickly and uniformly dispersed in the solution. Pure oxygen (flow rate 200ml/min) passes through an ozone generator to generate a mixed gas of oxygen and ozone, and the concentration of ozone in the mixed gas is 4.2 mg/L. The mixed gas is blown into the oxalic acid solution from the bottom of the reaction kettle through an aeration device, and the ozone blown into the oxalic acid solution is 50.4 mg/h. When in useAnd introducing mixed gas, starting timing, introducing ozone into the reaction system at the moment, and starting the ozone oxidation reaction of the oxalic acid. The reaction temperature is 20 ℃, the reaction time is 60min, and the oxalic acid removal rate is 48%.
Comparative example 3 ozone oxidation reaction of oxalic acid alone in Water
Taking 1L of oxalic acid solution with the concentration of 50mg/L, adding the oxalic acid solution into a 1.5L reaction kettle, and starting a stirring device at the speed of 150 r/min. Pure oxygen (flow rate 200ml/min) passes through an ozone generator to generate a mixed gas of oxygen and ozone, and the concentration of ozone in the mixed gas is 4.2 mg/L. The mixed gas is blown into the oxalic acid solution from the bottom of the reaction kettle through an aeration device, and the ozone blown into the oxalic acid solution is 50.4 mg/h. When the mixed gas is introduced, timing is started, ozone enters a reaction system at the moment, and the ozone oxidation reaction of the oxalic acid starts to occur. The reaction temperature is 20 ℃, the reaction time is 60min, and the oxalic acid removal rate is 11%.
Comparative examples 4 and V8C7Adsorption experiment of/CS on oxalic acid in water
Taking 1L of oxalic acid solution with the concentration of 50mg/L, adding the oxalic acid solution into a 1.5L reaction kettle, and starting a stirring device at the speed of 150 r/min. Then 50mg V is weighed8C7/CS (prepared in example 1) was added to the reaction vessel with stirring V8C7the/CS was rapidly and homogeneously dispersed in the solution. Pure oxygen (flow 200ml/min) is blown into the oxalic acid solution from the bottom of the reaction kettle through an aeration device, and the ozone blown into the oxalic acid solution is 0 because an ozone generating device is not started. When oxygen is introduced, timing is started. The adsorption temperature is 20 ℃, the adsorption time is 60min, and the oxalic acid removal rate is 8%.
Comparative example 5 Effect of radical inhibitor on oxalic acid catalyzed ozone Oxidation reaction in Water
Taking 1L oxalic acid solution with the concentration of 50mg/L, adding 50mg tert-butyl alcohol (free radical inhibitor), adding the mixed solution into a 1.5L reaction kettle, and starting a stirring device at the speed of 150 r/min. Then 50mg V is weighed8C7/CS (prepared in example 1) was added to the reaction vessel with stirring V8C7the/CS was rapidly and homogeneously dispersed in the solution. Pure oxygen (flow rate 200ml/min) passes through an ozone generator to generate a mixed gas of oxygen and ozone, and the concentration of ozone in the mixed gas is 4.2 mg/L. Mixing ofThe synthetic gas is blown into the oxalic acid solution from the bottom of the reaction kettle through an aeration device, and the ozone blown into the oxalic acid solution is 50.4 mg/h. When the mixed gas is introduced, timing is started, ozone enters a reaction system at the moment, and the ozone oxidation reaction of the oxalic acid starts to occur. The reaction temperature is 20 ℃, the reaction time is 60min, and the oxalic acid removal rate is 12%.
Comparative example 6 Effect of humic acid on ozone Oxidation reaction of oxalic acid alone in Water
Taking 1L of oxalic acid solution with the concentration of 50mg/L, adding 50mg of humic acid, adding the mixed solution into a 1.5L reaction kettle, and starting a stirring device at the speed of 150 r/min. Pure oxygen (flow rate 200ml/min) passes through an ozone generator to generate a mixed gas of oxygen and ozone, and the concentration of ozone in the mixed gas is 4.2 mg/L. The mixed gas is blown into the solution from the bottom of the reaction kettle through an aeration device, and the ozone blown into the mixed solution is 50.4 mg/h. When the mixed gas is introduced, timing is started, at this time, ozone enters the reaction system, and the ozone oxidation reaction starts to occur. The reaction temperature is 20 ℃, the reaction time is 60min, the oxalic acid is accumulated, the concentration is increased by 10 percent, and the removal rate of humic acid is 86 percent.
Comparative example 7 Effect of humic acid on catalytic ozonation of oxalic acid in Water
Taking 1L of oxalic acid solution with the concentration of 50mg/L, adding 50mg of humic acid, adding the mixed solution into a 1.5L reaction kettle, and starting a stirring device at the speed of 150 r/min. Then 50mg V is weighed8C7/CS (prepared in example 1) was added to the reaction vessel with stirring V8C7the/CS was rapidly and homogeneously dispersed in the solution. Pure oxygen (flow rate 200ml/min) passes through an ozone generator to generate a mixed gas of oxygen and ozone, and the concentration of ozone in the mixed gas is 4.2 mg/L. The mixed gas is blown into the solution from the bottom of the reaction kettle through an aeration device, and the ozone blown into the mixed solution is 50.4 mg/h. When the mixed gas is introduced, timing is started, at this time, ozone enters the reaction system, and the ozone oxidation reaction starts to occur. The reaction temperature is 20 ℃, the reaction time is 60min, the oxalic acid removal rate is 72 percent, and the humic acid removal rate is 91 percent.
FIG. 4 shows the results of the ozonation reaction of Oxalic Acid (OA) in water, showing the change of oxalic acid content with reaction time under different conditions, wherein the ordinate representsThe lower the ratio of the real-time concentration of oxalic acid in the solution to the initial concentration, the higher the oxalic acid removal rate. As can be seen from FIG. 4, in the ozone oxidation reaction alone (comparative example 3, black boxed line in FIG. 4, O)3) And V8C7Adsorption experiment of/CS on oxalic acid (comparative example 4, red line with five-pointed star in FIG. 4, O)2+V8C7CS), the removal rates of oxalic acid were all very low, 10 and 12% at 60 min. In comparison, V8C7Can catalyze the ozone oxidation reaction of oxalic acid in water (comparative example 2, rose red rhombus line in figure 4, O)3+V8C7) But the removal rate is lower, and the removal rate of oxalic acid is 48 percent at 60 min. The supported transition metal carbide V of the present invention8C7When the ozone oxidation reaction of oxalic acid in water is catalyzed by CS, the removal rate of oxalic acid is 95% at 60min (blue triangular line, O in example 1 and figure 4)3+V8C7/CS)，V8C7the/CS can catalyze the reaction more efficiently. In addition, free radical inhibitors (TBA) on V8C7the/CS catalyzed ozone oxidation reaction has extremely strong inhibition effect (comparative example 5, line of green circle in figure 4, O)3+V8C7/CS + TBA), which proves that V8C7the/CS accelerates the ozone oxidation reaction of the oxalic acid in the water by initiating a free radical reaction.
FIG. 5 is a graph showing a comparison of ozone utilization in the Oxalic Acid (OA) ozonation reaction in water. TOD in FIG. 5 is the ozone transfer amount, and the calculation method is as follows:
wherein: t represents a reaction time; c. CO3,inAnd cO3,outRespectively representing the ozone concentration of inlet gas and outlet gas; qGasRepresents the air flow rate, which is 200mL/min in this experiment; vLiquidRepresents the volume of the solution, which is 1L in this experiment.
SOZ in FIG. 5 represents the ozone oxidation process alone of oxalic acid (comparative example 3, black bar with squares representing) (ii) a COZ represents the supported transition metal carbide V of the present invention8C7the/CS catalyzed ozone oxidation process (example 1, blue bar, triangle line representation). As is clear from FIG. 5, supported transition metal carbide V according to the present invention8C7After the catalyst is used as the catalyst, the ozone utilization rate is far higher than that of a single ozone oxidation reaction without the catalyst, namely the oxalic acid removal rate is higher in the ozone oxidation process by using the catalyst of the invention under the same ozone transfer amount.
FIG. 6 shows the change of the concentration of oxalic acid and humic acid with the progress of the reaction in the single ozonation and catalytic ozonation of the mixed solution of oxalic acid and humic acid (in the figure, the blue-band square line shows the change of the concentration of oxalic acid in the single ozonation, comparative example 6; and the green-band circle line shows the load-type transition metal carbide V of the present invention8C7The change of the oxalic acid concentration in the CS catalytic ozonation process, comparative example 7; the solid square line of the black band indicates the change of the concentration of humic acid in the oxidation process of ozone alone, comparative example 6; the solid circle in the red color indicates the load type transition metal carbide V of the invention8C7Comparative example 7) change in humic acid concentration during catalytic ozonation by CS. As can be seen from fig. 6: in the single ozone oxidation process without adding a catalyst, humic acid in water is directly oxidized by ozone; however, since ozonation of humic acid alone has the accumulation of oxalic acid, and oxalic acid is difficult to be directly oxidized by ozone, the concentration of oxalic acid in water is slightly increased; adding the supported transition metal carbide V of the invention8C7In the catalytic ozonation process with/CS as a catalyst, not only can humic acid in water be quickly oxidized and removed by ozone, but also oxalic acid in water can be quickly oxidized and removed, V8C7The free radical reaction initiated by the CS can effectively remove the oxalic acid in the water.
The above examples and comparative examples illustrate the invention V8C7/CS、W2C/CS、Fe2The supported transition metal carbide catalyst such as C/CS has good catalytic activity for the ozone oxidation reaction of organic matters in water. Compared with the non-supported transition metal carbide and no metal addition of the comparative exampleThe carbon microsphere material prepared by the source is used as a catalyst, and the single ozone oxidation reaction without the catalyst is adopted, under the same condition, the supported transition metal carbide catalyzed ozone oxidation reaction realizes the optimal water treatment effect, and the oxalic acid removal rate is optimal. The addition of the free radical inhibitor tert-butyl alcohol has an inhibiting effect on the catalytic ozonation reaction, and proves that the catalytic ozonation reaction realizes a faster oxalic acid removal rate through the free radical reaction. This is due to the extremely slow direct reaction rate (reaction rate constant k) of oxalic acid with ozoneO3-OA≤0.04L·mol-1·s-1) And the reaction rate of oxalic acid with free radicals is extremely fast (reaction rate constant k)·OH-OA≈106L·mol-1·s-1). Therefore, oxalic acid is a typical intermediate product and is easily accumulated in the single ozone oxidation reaction of the organic wastewater. Also, ozone oxidation of oxalic acid has been shown to be a thorough mineralization process directly to carbon dioxide and water. Humic acid is added in the catalytic ozonation reaction of the oxalic acid, and the oxalic acid and the humic acid in the solution are reduced along with the reaction without accumulation of the oxalic acid. The results prove that: the catalytic ozonation reaction can indiscriminately oxidize organic matters in water, and the mineralization degree of the organic matters is high.
In conclusion, when the supported transition metal carbide is used as a catalyst to catalyze the ozone oxidation reaction of organic matters in water, a free radical reaction is initiated, the removal rate of the organic matters in the sewage is high, the removal rate is high, the mineralization degree is high, and the organic pollutants with complex types in the water can be selectively catalyzed and oxidized; meanwhile, when the catalyst is used, the ozone oxidation reaction can be carried out at room temperature, the time consumption is short, and the energy consumption is low; in addition, the preparation process of the load type transition metal carbide is simple and easy to form. The load type transition metal carbide can be used as a catalyst to relieve the problems of environment and energy, has strong practicability and good market prospect.
Claims (10)
1. A preparation method of supported transition metal carbide is characterized by comprising the following steps: it comprises the following steps: dissolving a carbon source and a transition metal salt in a solvent, carrying out solvothermal reaction to prepare a metal organic framework precursor, and then carbonizing to obtain the metal organic framework precursor.
2. The method of claim 1, wherein:
the carbon source is one or two of glucose, melamine or terephthalic acid;
and/or in the transition metal salt, the transition metal is vanadium, tungsten, iron, titanium, chromium, zirconium or niobium;
and/or the solvent is deionized water, ethanol or N, N-dimethylformamide;
and/or the mass ratio of the carbon source to the transition metal salt is 1: (0.05-0.5);
and/or the mass volume ratio of the carbon source to the solvent is (1-5) g: (10-100) mL.
3. The method of claim 2, wherein:
the carbon source is glucose;
and/or the transition metal salt is ammonium metavanadate, phosphotungstic acid, ferric nitrate, titanium tetrachloride, chromium chloride, zirconium chloride or niobium chloride;
and/or the solvent is deionized water;
and/or the mass ratio of the carbon source to the transition metal salt is 1: (0.1 to 0.3);
and/or the mass volume ratio of the carbon source to the solvent is 1 g: 10 mL.
4. The production method according to claim 3, characterized in that:
the transition metal salt is ammonium metavanadate;
and/or the mass ratio of the carbon source to the transition metal salt is 1: (0.12-0.27).
5. The method of claim 1, wherein:
when the mixture is dissolved in the solvent, the temperature of the solvent is 50-100 ℃, and the mixture is stirred for 1-5 hours;
and/or the hydrothermal reaction condition is that the reaction is carried out for 12-24 hours at the temperature of 140-220 ℃;
and/or cleaning and drying the prepared metal organic framework precursor after the hydrothermal reaction;
and/or the carbonization condition is carbonization in an inert atmosphere.
6. A supported transition metal carbide characterized by: it is transition metal carbide nano-particles loaded on a carbon microsphere carrier.
7. The supported transition metal carbide of claim 6, wherein: the supported transition metal carbide is prepared by the preparation method of any one of claims 1 to 5.
8. Use of a supported transition metal carbide according to claim 6 or 7 as a catalyst: the catalyst is used for catalyzing the ozone oxidation reaction of organic pollutants in water;
preferably, the organic contaminants are selected from phenolic and/or carboxylic organic contaminants;
more preferably, the organic contaminant is oxalic acid and/or humic acid.
9. Use of a supported transition metal carbide according to claim 6 or 7 in the preparation of a catalyst: the catalyst is used for catalyzing the ozone oxidation reaction of organic pollutants in water;
preferably, the organic contaminants are selected from phenolic and/or carboxylic organic contaminants;
more preferably, the organic contaminant is oxalic acid and/or humic acid.
10. Use of a transition metal carbide as a catalyst and/or in the preparation of a catalyst; the catalyst is used for catalyzing the ozone oxidation reaction of organic pollutants in water;
preferably, the organic contaminants are selected from phenolic and/or carboxylic organic contaminants;
and/or the transition metal carbide is vanadium carbide, tungsten carbide, iron carbide, titanium carbide, chromium carbide, zirconium carbide or niobium carbide;
more preferably, the organic contaminant is oxalic acid and/or humic acid;
and/or the transition metal carbide is vanadium carbide.
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| CN114180965A (en) * | 2021-12-27 | 2022-03-15 | 安徽工业大学 | High-entropy carbide nano powder material with high sphericity and high activity, and preparation method and application thereof |
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| CN114984990A (en) * | 2022-05-16 | 2022-09-02 | 湖南大学 | Tubular carbon nitride-based Schottky heterojunction photocatalyst and preparation method and application thereof |
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